JP2010209139A - Furan-based resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin which uses a biomass as a raw material, and is excellent in heat resistance, mechanical strengths and durability. <P>SOLUTION: There is provided a furan-based resin having furan structures of general formula (1) and the like, and generically called polyketones, polyethers, polythioethers, polycarbonates, or polyurethanes. The resin is excellent in heat resistance, mechanical strengths, and durability, can be produced from agricultural wastes originated from plants of biomass as a raw material, and is an industrially useful resin capable of contributing also to environmental problems and global warming problems. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a furan resin that can be produced from a raw material derived from biomass and is excellent in heat resistance, mechanical strength, and durability. Specifically, the present invention relates to a furan resin in which a ketone structure, an ether structure, a thioether structure, a carbonate structure, and a urethane structure are introduced into the main chain.

  Recently, biodegradable resins and resins using biomass-derived materials have been developed and put into practical use as environmentally friendly or environmentally sustainable materials. Compared to general-purpose resins and engineering plastics, the current situation is that they cannot be said to be superior in terms of heat resistance, mechanical strength, durability, molding processability, and manufacturing cost.

  Among them, it is worth noting that excellent heat resistance and mechanical strength have been reported for some resins selected from raw materials of furan derivatives that can be produced from biomass (see Patent Documents 1 and 2 and Non-Patent Document 1). To 3). However, in such resins collectively called polyesters and polyamides in which the furan structure is introduced into the main chain by ester bonds, hydrolysis of ester bonds or amide bonds may proceed due to moisture in the air or the like. There are challenges. Further, in order to use it as an electrical / electronic component, automobile material, and engineering component-related material, further improvements regarding heat resistance, mechanical strength, durability, molding processability, and manufacturing cost are required.

JP2008-291243 JP 2008-291244 A

Gardini, A., Macromol., 41, 3949 (2008) Gardini, A., et al., Prog. Polym. Sci., 22,1203 (1997) Belgacem, M.N., Gardini, A., Eds., Monomers, Polymers and Compositesfrom Renewable Resources, Elsevier, Amsterdam, 2008

  An object of the present invention is to provide a resin excellent in heat resistance, mechanical strength, and weather resistance, which can be produced from a raw material derived from biomass. Specifically, an industry that contributes to environmental and global warming issues by producing resins with excellent heat resistance, mechanical properties, and durability using furan derivatives that can be produced from discarded plant-derived agricultural waste. It is to provide a useful resin.

  As a result of diligent studies to solve the above problems, the present inventors have found that a furan resin in which a ketone structure, an ether structure, a thioether structure, a sulfone structure, a carbonate structure, and a urethane structure are introduced into the main chain has a biomass. It has been found that it can be produced as a raw material and exhibits various excellent characteristics, and the present invention has been completed.

  That is, the present invention is characterized by the matters described in [1] to [3] below.

上記一般式（１）又は（２）において、Ｐは、ＣＯ、Ｏ、S、ＯＣＯＯ又はＮＨＣＯＯのいずれかであり、上記一般式（２）において、Ｒ及びＲ’は、ＣｍＨｍ（ｍは１０以下の正の整数）である。 [1] A furan resin having the following general formula (1) or (2) as a unit structure.

In the general formula (1) or (2), P is any one of CO, O, S, OCOO, and NHCOO. In the general formula (2), R and R ′ are CmHm (m is 10 or less). Positive integer).

Although the substituent of the furan structure represented by the general formula (1) or (2) has been introduced in two places, the substituent of the furan-based resin is any one of the 2-position to 5-position. It can be introduced above.

[2] A furan resin obtained by copolymerization so as to have two or more unit structures of the general formula (1) and / or (2) described in [1].

[3] The content of the component comprising at least one unit structure of the general formula (1) and / or at least one unit structure of (2) according to the above [1] is 50% by weight or more of the total components A furan resin characterized by being.

上記一般式（３）又は（４）において、Ｐは、ＣＯ、Ｏ、S、ＯＣＯＯ又はＮＨＣＯＯのいずれかであり、上記一般式（２）において、Ｒ及びＲ’は、ＣｍＨｍ（ｍは１０以下の正の整数）である。 [4] The above-mentioned [1] to [3], wherein the unit structure of the general formula (1) or (2) described in [1] is the following general formula (3) or (4) One of our furan resins.

In the general formula (3) or (4), P is any one of CO, O, S, OCOO, and NHCOO. In the general formula (2), R and R ′ are CmHm (m is 10 or less). Positive integer).

  According to the present invention, it is possible to provide an industrially useful resin having excellent heat resistance, mechanical strength, and durability using biomass as a raw material.

  In particular, the provision of industrially useful resins with excellent heat resistance, mechanical strength, and durability using furan derivatives that can be produced from plant-derived agricultural waste that is not effectively used and discarded Enable.

  Below, the typical aspect for implementing this invention is demonstrated concretely, However, This invention is not limited to the following aspects, unless the summary is exceeded.

  The position of the substituent of the furan structure represented by the general formula (1) or (2) may be introduced at two or more of any of the 2nd to 5th positions. Among these, those introduced at two positions of the 2nd and 5th positions are most preferable. When three or more substituents in the furan structure cause a polymerization reaction, it may be necessary to pay attention to gelation of the resulting resin due to the progress of crosslinking depending on the combination of the substituents.

<Monomer component constituting the resin provided by the present invention>
As typical examples of the monomer component constituting the resin provided by the present invention, the following compounds [A] to [N] in which substituents are introduced at the 2-position and / or 5-position of the furan structure are exemplified. In addition to these examples, those having one or more substituents introduced at the 2nd to 5th positions can be used. These monomer components are all furan derivatives that can be produced from plant-derived agricultural waste materials.

  The monomer component having a furan structure constituting the resin provided by the present invention may be used alone or in combination of two or more. A copolymer (copolymer) obtained by using two or more kinds of monomer components in combination, that is, the furan resin described in [2] is a homopolymer ([1 It is often important to exhibit balanced properties as compared to the furan-based resins described in 1).

  The monomer component having a furan structure constituting the resin provided by the present invention may be manufactured from petroleum-derived raw materials or biomass-derived raw materials. However, when considering contribution to environmental problems, the monomer components must be manufactured from biomass-derived raw materials. Don't be.

<The manufacturing method of the furan-type resin as described in [1] provided by the present invention>
The resin described in [1] is a resin collectively referred to as polyketone, polyether, polythioether, polysulfone, polycarbonate, and polyurethane.
Below, the manufacturing method of each resin which introduce | transduced the substituent into 2-position and 5-position of the furan structure which is the most preferable form is shown.

<< Polyketone >>
The following reaction can be exemplified as a synthesis method of the polyketone resin provided by the present invention (when P in the general formulas (1) and (2) of the unit structure is CO)). It can be obtained by proceeding Friedel-Craft reaction of 2-furancarboxylic acid chloride (compound [F]) with a catalyst typified by AlCl3. It can also be obtained by allowing Friedel-Craft reaction to proceed with furan (compound [A]) and 2,5-furandicarboxylic acid chloride (compound [G]) with a catalyst typified by AlCl3.

  Polyketone is characterized by low hydrolyzability and excellent heat resistance and mechanical strength when compared to polyester.

<< Polyether >>
The following reaction can be exemplified as a method for synthesizing the polyether provided by the present invention (when P in the general formulas (1) and (2) of the unit structure is O). 2,5-dimethylolfuran (compound [I]) is reacted with 2,5-dihalomethylfuran (compound [M]) after converting the hydroxyl group to NaO— (sodium alcoholate) using NaH. , Desalted NaX (X represents a halogen atom) is allowed to proceed and condensed.
In addition, 2,5-dimethylolfuran (compound [I]) is reacted with 2,5-dihalofuran (compound [L]) after converting the hydroxyl group to NaO— (sodium alcoholate) using NaH. It can also be obtained by allowing desalted NaX (X represents a halogen atom) to proceed and condense.
Polyethers are characterized by low hydrolyzability and excellent thermal processability when compared to polyester.

<< Polythioether >>
The following reaction can be exemplified as a synthesis method of the polythioether provided by the present invention (when P in the general formulas (1) and (2) of the unit structure is S)). It can be obtained by condensing 2,5-dihalofuran (compound [L]) by proceeding with desalted NaX (X represents a halogen atom) in the presence of Na2S.
It can also be obtained by condensing 2,5-dichloromethylfuran obtained by reacting 2,5-dimethylolfuran (compound [M]) with chlorine by proceeding with desalted NaCl in the presence of Na2S. It is done.
Polythioether has characteristics of low hydrolyzability, high heat resistance and mechanical strength, and excellent compatibility with other materials when compared with polyester.

<< Polycarbonate >>
The following reaction can be exemplified as a synthesis method of the polycarbonate provided by the present invention (when P in the general formulas (1) and (2) of the unit structure is SO2)).
It can be obtained by reacting 2,5-dimethylolfuran (compound [I]) with phosgene and condensing while dehydrochlorinating.

It is noted that polycarbonate has higher heat resistance and mechanical strength, particularly impact resistance, when compared to polyester. Furthermore, it is also important to have excellent optical properties, particularly transparency.
<< Polyurethane >>

  Polysulfone corresponding to the general formula (1) in the polyurethane provided by the present invention (when P in the unit structure general formulas (1) and (2) is OCONH) (when P in the unit structure general formula (1) is OCONH) The following reaction can be illustrated as a synthesis method of). Obtained by reacting 2,5-dimethylolfuran (compound [I]) with a bifunctional or higher isocyanate compound, such as toluene diisocyanate, and addition-condensation with or without a catalyst represented by tin octylate. It is done.

  The same is true not only in comparison with polyester but also in comparison with other resins, but the synthesis of polyurethane is relatively easy, which greatly contributes to the industrial importance of this material. However, at present, half of the material needs to use petroleum-derived compounds.

  Of the above [1], the furan-based resin having the general formula (2) as a unit structure has a structure corresponding to R and R ′ in the general formula (2) generically called an aliphatic hydrocarbon. It has a very important influence on the mechanical strength of the polymer provided by the invention. That is, as the m of CmHm as R and R ′ increases, the elastic modulus decreases, but the elongation increases and so-called toughness may be added. Furthermore, the melt viscosity at the time of heating is reduced, which is advantageous in terms of molding processing, and the hydrophobicity is increased, which is advantageous in applications in which water absorption and moisture absorption are important.

<The manufacturing method of the furan-type resin as described in said [2] which this invention provides>
Next, a typical method for synthesizing a furan resin, which is copolymerized so as to have two or more unit structures represented by the general formula (1) and / or (2) described in [1] above, will be described.

<< Binary copolymer of polyketone and polyether >>
A polyketone provided by the present invention (when P in the general formulas (1) and (2) of the unit structure is CO) and a polyether (when P in the general formulas (1) and (2) of the unit structure are O) The following reaction can be illustrated as a polymer synthesis method. 2,5-dimethylolfuran (compound [I]) is reacted with di (2-halofuranyl) ketone (compound [N]) after converting the hydroxyl group to NaO— (sodium alcoholate) using NaH, It is obtained by allowing desalted NaX (X represents a halogen atom) to proceed and condense.

<< Binary copolymer of polyketone and polythioether >>
The polyketone provided by the present invention (when P in the general formulas (1) and (2) of the unit structure is CO) and polythioether (when P in the general formulas (1) and (2) of the unit structure are S) The following reaction can be illustrated as a polymer synthesis method. It can be obtained by condensing di (2-halofuranyl) ketone (compound [N]) by proceeding with desalted NaX (X represents a halogen atom) in the presence of Na 2 S.

P、Q、および、Rは、-Z-F、-Z-Cl、-Z-Br、-Z-I、-Z-OH、-Z-CHO、-Z-COOH、-Z-COOR、-Z-COCl、-Z-CONHR、-Z-CONRR’、-Z-NH2、-Z-NHR、-ZNRR’、-Z-NO2、-Z-CM、および、-CmH2m+1を表す。 ここで、Zは、なし、-CH2-または-C2H4-を表し、ｍは０または１０以下の自然数を表す。 <The manufacturing method of the furan resin as described in [3] provided by the present invention>
The furan-based resin provided by the present invention may be copolymerized with various monomers not containing a furan structure as long as the characteristics are not impaired. When the typical thing of the copolymerizable monomer which does not contain a furan structure is illustrated, the compound group shown to the following trifunctional formula (a)-(h) will be mentioned. However, 4- to 6-functional compound groups can be used as long as the characteristics are not impaired. These compounds may be used alone or in combination.

P, Q, and R are -ZF, -Z-Cl, -Z-Br, -ZI, -Z-OH, -Z-CHO, -Z-COOH, -Z-COOR, -Z-COCl, -Z-CONHR, -Z-CONRR ', -Z-NH2, -Z-NHR, -ZNRR', -Z-NO2, -Z-CM, and -CmH2m + 1 are represented. Here, Z represents none, —CH 2 — or —C 2 H 4 —, and m represents a natural number of 0 or 10 or less.

  If the proportion of the monomer component having a furan structure constituting the resin provided by the present invention is less than 50% by weight, the excellent characteristics resulting from the special furan structure, which is a feature of the present invention, cannot necessarily be expressed. 1) the content of the component comprising one or more unit structures of the general formula (1) and / or one or more unit structures of (2) must be 50% by weight or more of the total components, More preferably, it is 70% by weight or more. When the copolymer component is produced from petroleum-derived raw materials, the contribution to environmental problems is also reduced.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded. In addition, the measurement methods and molding methods for various physical properties and the like in the following are as follows.

Tensile test: A press film was prepared using the resins obtained in the examples and comparative examples, a sample was punched out into a dumbbell shape from the obtained press film, and a tensile tester (precision universal testing machine Autograph AG-) was formed according to JIS K7127. X, manufactured by Shimadzu Corporation) was subjected to a tensile test, and the tensile modulus was measured.
Thermal analysis: Melting temperature was measured with a thermal analyzer (Thermoplus DSC 8230, manufactured by Rigaku) using the resins obtained in Examples and Comparative Examples.

攪拌機、窒素導入口、マントルヒータ、温度計、および、冷却管を装着した反応容器を減圧置換で窒素雰囲気にした後、２−フランカルボン酸１００ｇ、キノリン０．５ｇ、および、銅０．５ｇを攪拌子と共に仕込み、室温で１０時間加熱攪拌した。得られた反応液を蒸留して収率７０％でフランを得た（４３℃、常圧）。冷却管と滴下ロートを装着した丸底フラスコにＴＨＦ１００ｍＬとフラン１０ｇ（１４７ｍｍｏｌ）を仕込み、氷冷下、滴下ロートから臭素２３．５ｇ（１４７ｍｍｏｌ）を３０分かけて滴下した。さらに室温で５時間攪拌を継続した。得られた反応液を分液ロートに移し、トルエン５００ｍＬと純水５００ｍＬを加えて良くしんとうした。水層を除去して再び純水５００ｍＬを加えて良くしんとうした。有機層を取り出しＭｇＳＯ４で脱水後、濃縮乾燥した。得られた固形分をトルエン／メタノール混合溶媒で再結晶することで高純度の２，５−ジブロモフランを得た（得量３０．３ｇ、収率８０％ ）。攪拌機、窒素導入口、マントルヒータ、温度計、および、冷却管を装着した反応容器を減圧置換で窒素雰囲気にして、得られた２，５−ジブロモフラン２０ｇ（７７．５ｍｍｏｌ）、Ｎ−メチルピロリドン２００ｍＬ、および、Ｎａ２Ｓ６．０ｇ（７７．５ｍｍｏｌ）を添加して１５０℃で１０時間加熱を続けた。反応容器内の混合液を大量のメタノールに滴下し発生した沈澱を濾過にて回収した。６０℃の通風乾燥機で乾燥後、大量の純水で洗浄した。固形分を濾過にて回収し再度６０℃の通風乾燥機で１日乾燥して目的の樹脂を得た（得量４．５６ｇ、収率６０％）。得られた樹脂の引張弾性率は５８００ＭＰａ、溶融温度は、３００℃以上であった。 [Example 1]

A reaction vessel equipped with a stirrer, a nitrogen inlet, a mantle heater, a thermometer, and a cooling tube was placed under a nitrogen atmosphere by vacuum replacement, and then 100 g of 2-furancarboxylic acid, 0.5 g of quinoline, and 0.5 g of copper were added. The mixture was charged with a stirrer and heated and stirred at room temperature for 10 hours. The obtained reaction solution was distilled to obtain furan in a yield of 70% (43 ° C., normal pressure). A round bottom flask equipped with a condenser and a dropping funnel was charged with 100 mL of THF and 10 g (147 mmol) of furan, and 23.5 g (147 mmol) of bromine was added dropwise from the dropping funnel over 30 minutes under ice cooling. Further, stirring was continued at room temperature for 5 hours. The obtained reaction solution was transferred to a separatory funnel, and 500 mL of toluene and 500 mL of pure water were added and well squeezed. The aqueous layer was removed, and 500 mL of pure water was added again, and the mixture was well reinforced. The organic layer was taken out, dehydrated with MgSO4, and concentrated to dryness. The obtained solid was recrystallized with a toluene / methanol mixed solvent to obtain 2,5-dibromofuran of high purity (amount 30.3 g, yield 80%). A reaction vessel equipped with a stirrer, a nitrogen inlet, a mantle heater, a thermometer, and a cooling tube was placed in a nitrogen atmosphere by substituting under reduced pressure, and 20 g (77.5 mmol) of the obtained 2,5-dibromofuran was obtained. 200 mL and 6.0 g (77.5 mmol) of Na 2 S were added and heating was continued at 150 ° C. for 10 hours. The mixed solution in the reaction vessel was dropped into a large amount of methanol, and the generated precipitate was collected by filtration. After drying with a ventilation dryer at 60 ° C., it was washed with a large amount of pure water. The solid content was collected by filtration and again dried for 1 day with a draft dryer at 60 ° C. to obtain the desired resin (yield 4.56 g, yield 60%). The obtained resin had a tensile modulus of 5800 MPa and a melting temperature of 300 ° C. or higher.

攪拌機、窒素導入口、マントルヒータ、温度計、および、冷却管を装着した反応容器を減圧置換で窒素雰囲気にした後、２，５−フランジカルボン酸１０ｇ（６４．１ｍｍｏｌ）に塩化チオニル１００ｍＬを加えて８０℃で３時間反応させた後、濃縮乾燥し２，５−フランジカルボン酸クロライド１２．３ｇを得た。攪拌装置、窒素導入口、加熱装置、温度計、および、冷却管を装着した反応容器を減圧置換で窒素雰囲気にした後、得られた２，５−フランジカルボン酸クロライド１０．０ｇ（５１．８ｍｍｏｌ）、フラン３．５２ｇ（５１．８ｍｍｏｌ）、Ｎ−メチルピロリドン１００ｍＬ、および、ＡｌＣｌ3、７．６４ｇ（５７．０ｍｍｏｌ）を添加し、７０℃で２０時間反応を継続した。反応容器内の混合液を大量のメタノールに滴下し発生した沈澱を濾過にて回収した。６０℃の通風乾燥機で１日乾燥して目的の樹脂を得た（得量３．１６ｇ、収率６５％）。得られた樹脂の引張弾性率は５２００ＭＰａ、溶融温度は、２９０℃であった。 [Example 2]

A reaction vessel equipped with a stirrer, nitrogen inlet, mantle heater, thermometer, and cooling tube was placed under a nitrogen atmosphere by vacuum replacement, and then 100 mL of thionyl chloride was added to 10 g (64.1 mmol) of 2,5-furandicarboxylic acid. The mixture was reacted at 80 ° C. for 3 hours and then concentrated to dryness to obtain 12.3 g of 2,5-furandicarboxylic acid chloride. A reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer, and a cooling tube was placed in a nitrogen atmosphere by vacuum replacement, and then 10.0 g (51.8 mmol) of 2,5-furandicarboxylic acid chloride obtained was obtained. ), 3.52 g (51.8 mmol) of furan, 100 mL of N-methylpyrrolidone, and 7.64 g (57.0 mmol) of AlCl 3 were added, and the reaction was continued at 70 ° C. for 20 hours. The mixed solution in the reaction vessel was dropped into a large amount of methanol, and the generated precipitate was collected by filtration. The desired resin was obtained by drying for 1 day with a 60 ° C. ventilation dryer (yield 3.16 g, yield 65%). The obtained resin had a tensile modulus of 5200 MPa and a melting temperature of 290 ° C.

攪拌機、窒素導入口、マントルヒータ、温度計、および、冷却管を装着した反応容器を減圧置換で窒素雰囲気にした後、２，５−ジメチロールフラン１０ｇ（１００ｍｍｏｌ）、トリエチルアミン９．７２ｇ（１２０ｍｍｏｌ）、および、ＴＨＦ１００ｇを攪拌子と共に仕込み、激しく攪拌しながらホスゲン９．９０ｇ（１００ｍｍｏｌ）を注意深くゆっくりと反応容器に仕込んだ。室温で２時間攪拌後、６０℃に昇温してさらに４時間攪拌を続けた。反応液を大量のメタノールに滴下して得られた沈澱を濾過にて回収し乾燥することで目的の樹脂を得た（得量１０．８ｇ、収率７０％）。得られた樹脂の引張弾性率は２１００ＭＰａ、溶融温度１９０℃であった。 Example 3

A reaction vessel equipped with a stirrer, a nitrogen inlet, a mantle heater, a thermometer, and a cooling pipe was made into a nitrogen atmosphere by vacuum replacement, and then 2,5-dimethylolfuran 10 g (100 mmol), triethylamine 9.72 g (120 mmol) Then, 100 g of THF was charged together with a stirring bar, and 9.90 g (100 mmol) of phosgene was carefully and slowly charged into the reaction vessel with vigorous stirring. After stirring at room temperature for 2 hours, the temperature was raised to 60 ° C. and stirring was continued for 4 hours. The precipitate obtained by dropping the reaction solution into a large amount of methanol was collected by filtration and dried to obtain the desired resin (yield 10.8 g, yield 70%). The obtained resin had a tensile modulus of 2100 MPa and a melting temperature of 190 ° C.

攪拌機、窒素導入口、マントルヒータ、温度計、および、冷却管を装着した反応容器を減圧置換で窒素雰囲気にした後、２，５−ジメチロールフラン１０ｇ（１００ｍｍｏｌ）、ＮａＨ2．６４ｇ（１１０ｍｍｏｌ）、および、ジメチルホルムアミド（ＤＭＦ）１００ｍＬを攪拌子と共に仕込んだ。 続いて、２、５−ジブロモフラン２２．２ｇ（１００ｍｍｏｌ）を注意深くゆっくりと反応容器に仕込んだ。６０℃に昇温して３時間攪拌を続けた。反応液を大量のメタノールに滴下して得られた沈澱を濾過にて回収し乾燥することで目的の樹脂を得た（得量１２．３ｇ、収率７０％）。得られた樹脂の引張弾性率は２６００ＭＰａ、溶融温度は２１０℃であった。 Example 4

A reaction vessel equipped with a stirrer, a nitrogen inlet, a mantle heater, a thermometer, and a cooling tube was placed under a nitrogen atmosphere by vacuum replacement, and then 2,5-dimethylolfuran 10 g (100 mmol), NaH 2 .64 g (110 mmol), And 100 mL of dimethylformamide (DMF) was charged with a stirring bar. Subsequently, 22.5-g (100 mmol) of 2,5-dibromofuran was carefully and slowly charged into the reaction vessel. The temperature was raised to 60 ° C. and stirring was continued for 3 hours. A precipitate obtained by dropping the reaction solution into a large amount of methanol was collected by filtration and dried to obtain the desired resin (yield 12.3 g, yield 70%). The resulting resin had a tensile modulus of 2600 MPa and a melting temperature of 210 ° C.

攪拌機、窒素導入口、マントルヒータ、温度計、および、冷却管を装着した反応容器を減圧置換で窒素雰囲気にした後、ジメチル−２，５−フランジカルボン酸２０．０ｇ、１，４−ブタンジオール２４．１ｇ、チタンテトラブチレート１９．１ｍｇ、および、酢酸マグネシウム４水和物１１．９ｍｇを仕込んだ。２２０℃に昇温し２時間反応した後、２４０℃に昇温し、さらに反応容器内を十分減圧した状態で５時間反応を継続した。得られた樹脂の引張弾性率は１２００ＭＰａ、溶融温度は１７０℃であった。 [Comparative Example 1]

A reaction vessel equipped with a stirrer, a nitrogen inlet, a mantle heater, a thermometer, and a cooling pipe was made into a nitrogen atmosphere by vacuum replacement, and then 20.0 g of dimethyl-2,5-furandicarboxylic acid, 1,4-butanediol 24.1 g, titanium tetrabutyrate 19.1 mg, and magnesium acetate tetrahydrate 11.9 mg were charged. After raising the temperature to 220 ° C. and reacting for 2 hours, the temperature was raised to 240 ° C., and the reaction was continued for 5 hours in a state where the pressure in the reaction vessel was sufficiently reduced. The resulting resin had a tensile modulus of 1200 MPa and a melting temperature of 170 ° C.

  As shown in Table 1, according to the present invention, a furan resin exhibiting excellent heat resistance, mechanical strength, and durability can be provided.

  If the resin group manufactured from petroleum-derived raw materials and currently used as general-purpose resins and engineering plastics can be replaced with furan-based resins manufactured from biomass-derived raw materials described in this case, which are environmentally friendly or environmentally sustainable materials It is extremely useful for industry.

Similarly, aliphatic resins represented by polylactic acid produced from biomass-derived raw materials do not necessarily have industrially satisfactory characteristics, and are produced from these and biomass-derived raw materials described in this case. It can be said that the furan resin is in a complementary position. It is expected to be applied as an environmentally friendly 21st century resin.
The furan resin of the present invention can be used in various ways as a resin composition to which various additives are added. In addition, various molding methods applied to general-purpose plastics can be applied to the furan resin of the present invention, and the resin and resin composition of the present invention can be processed into a molded body by these molding methods.

Claims (4)

Furan resin having the following general formula (1) or (2) as a unit structure.

In the general formula (1) or (2), P is any one of CO, O, S, OCOO, and NHCOO. In the general formula (2), R and R ′ are CmHm (m is 10 or less). Positive integer).
A furan-based resin obtained by copolymerization so as to have two or more unit structures of the general formula (1) and / or (2) according to claim 1.
The content of a component comprising one or more unit structures of the general formula (1) according to claim 1 and / or one or more unit structures of (2) is 50% by weight or more of all components. Furan resin.
The furan resin according to any one of claims 1 to 3, wherein the unit structure of the general formula (1) or (2) according to claim 1 is the following general formula (3) or (4). .

In the general formula (3) or (4), P is any one of CO, O, S, OCOO, and NHCOO. In the general formula (2), R and R ′ are CmHm (m is 10 or less). Positive integer).